Blown wrinkle varnish base



Patented Feb. 19, 1946 J BLOWN WRINKLE VARNISH BASE William A. Waldie,Oakwood, Ohio, assignor to New Wrinkle, Inc., Dayton, Ohio, acorporation of Delaware No Drawing. Original application December 22,

1941, Serial No. 424,010. Divided and this application October 26, 1942,Serial No. 463,443

2 Claims.

This invention relates to wrinkle varnish base, and this application isa division of my copending application Serial No. 424,010, now PatentNo. filed December 22, 1941, as a continuation-impart of applicationSerial No. 335,615, filed May 16, 1940.

The primary purpose of this invention is the preparation of a wrinklevarnish base comprising the reaction product of drying oil, oil solubleresin and air at elevated temperature.

Hitherto the preparation of wrinkle varnish base has been considered torequire the use or China-wood oil, oiticica oil and other similar dryingoils containing conjugated double bonds, or mixtures of them. These oilsor mixtures were generally used either in their raw or natural state orsubsequent to preliminary treatment as by blowing, depending on theparticular characteris-' tics required in the finished wrinkle varnishbase and the nature of the individual oil or mixture of oils being used.

More recently, as disclosed in copending application Serial No. 312,742,filed January 6, 1940, use has been made of blown dehydrated castor oilas a substitute for the costly drying oils previously used in thepreparation of wrinkle varnish base. i r

I have discovered that a wrinkle varnish base can be produced bychemically combining unblown dryingtype oil with oil soluble resin andair at elevated temperature. The resulting product exhibits excellentwrinkling-tendency with the addition of a small amount of drier in theusual manner, and the resultin composition produces a durable finishparticularly characterized by its hardness and toughness.

As typical examples of formulation and procedures according to myinvention, but Without thereby limitingmyself to the specificdetails ofprocedure and proportions indicated; the following illustrative examplesare-given:

Example I Maleic acid resin pounds 100-125 Dehydrated Castor oi'lgallons- 10- 12 Mineral-spirit; do 5- 8 Coal tar solvent; do l- 2 Themixture is allowed to cool to approximately i 400 F. whereupon air isblown through it and the mixture kept at a temperature ranging between375.and 400 F. The air blowing is continued for approximately one hour,and, the blown mixture isthen allowed to cool down to a temperature ofapproximately 300 F., whereupon the solvents are added.

The maleic acid resin may be of the type commercially available and soldunder trade names such as Amberol 801, Beckacite 1110, lBeckaci'te 1111and Beckacite 1114 all of which are maleic acid treated rosin glycerineresins, but, of course, other alkyd resins made from combination ofrosin, glycerine and polybasic acid or anhydride prove suitable.

Example II Amberol 801 pounds Varnish grade linseed oil gall'ons 12Mineral spirit do 5 v Solvesso #2 do 16 Nuodex cobalt 6% 1do ,4;

In preparing the wrinkle varnish base fromthe above components, theresin is first melted i'rrfour gallons of oil by heating to atemperature of ap-" proximately 540 F. The balance of the oil is then 3added and the mixture heated to approximately 400 F. Air is then blownthrough the mixtureto. produce vigorous agitation and the temperaturemaintained within a range of from 375 to 400 F. until the desiredviscosity is obtained; A satisfactory viscosity or end-point may beconsidered to have been reached when a drop falls froma stirring rodwith a slight thread-like filament while hot. When this condition hasbeen reached the mixture is withdrawn from the fire and the solvent anddrier added thereto. 1

In this instance, the mineral spirit is that-grade of petroleum productof either a paraffinic or naphthenic origin which is commonly known inthe trade as turpentine substitute, while Solvesso' #2 is a hydrogenatednaphtha having a volatility similar to that of xylol and manufactured byStandard Oil Company. Nuodex cob'alt 6% is a cobalt naphthenate driersolution in. which the metallic cobalt amounts to about 6%.

The end-point for the blowing step maybe de termined as previouslymentioned; however, it

, may also be determined by other means, asyfor instance, by withdrawingtest samples from time to time during the blowing operation, adding apredetermined amount of thinner to a definite weight of sample andcomparing the viscosity of the resulting solution with the Gardner-Holdtviscosity standards.

lons of the oil by heating to approximately 580 F. The mixture is thenremoved from the fire and the balance of the oil added to it and thewhole then heated to approximately 400 F. The

temperature is held between 375 and 400 F. and air blown through themixture until the proper viscosity has been attained. The blown mixtureis then removed from the fire and the mineral spirit added thereto. Thethinned mixture is further dilutedby adding the toluol as soon as thetemperature has dropped to at least 300 F., at which time the cobaltdrier is also added.

It will be noted that Amberol F-7 used in Example III is a rosinmodified phenol-formaldehyde type of resin and, therefore, those skilledin the art will understand that other oil soluble and non-reactivephenol-aldehyde resins of the same general characteristics may be usedin the practice of my invention. These include resins known bytradenames such as Beckacite, Durez, Paradura, Durite, Locto, Paranol,Varcum, etc. In every case an oil soluble and non-reactive quality 7must be employed.

The fundamental difference between the method of my invention and theproduct resulting from the practice thereof and the methods and productsof the prior art resides in the fact that wrinkle varnish bases hithertoproduced are characterized by the fact that they yield softer films atthe sameloil lengths than the wrinkle varnish base of my invention.Furthermore, the blown oils commonly used in the prior art exhibitautooxidizing tendencies due to the fact that they containintermolecularly dispersed air which results in gradual and continuousoxidation and ultimately leads to separation of part of the oil as aninsoluble gel thus rendering the product valueless for use in a varnishand particularly so when the varnish is part of a sprayable composition.

In contradistinction, the product of my invention will preserve itshomogeneous nature and will show no separationvfor an indefinite periodof time- I am unable to offer proof as to the mechanism of the reactionwhich the oil undergoes when treated with air at elevated temperature inthe presence of the synthetic resin as hereinbefore set forth, but it ismy opinion that due to the comparatively high temperature used in theblowing operation only that'air which is chemically taken up by themixture remains in the oil, the temperature of treatment beingsufficiently high to expel any non-combined air, thereby preventing theintermolecular dispersion'which appears to be present in the case ofblown oils.

According to my invention, oil, as such, is not used in the preparationof the final'wrinkle compositionfor it will be remembered that the oiland synthetic resin are'conjointly aerated. In other words, the oilitself is not subjected to blowing but rather the combination of oil andsynthetic resin,v which appears to produce a new product which exhibitsnovel'and valuable characteristics.

The selection of thinners is not critical although preference should begiven to those products of high volatility such as toluol, xylol, lightnaphtha, etc. Of course, a small quantity of low volatile solvent mayprove of value to bring about a sudden chilling of a batch in order tocheck the bodying thereof in the event that it should have been blown atrifle too long.

Likewise, many different driers may be used but preference should begiven to those commonly known as top driers? and which tend to form thesurface skin which is so desirable in wrinkle compositions. Theresinate, linoleate or naphthenate type of drier, characterized by readysolubility, proves very suitable for this purpose.

It will be understood that instead'of the de hydrated castor oil andvarnish grade linseed oil used in the examples tung oil, perilla oil,v

oiticica oil, soya bean oil, fish oil and other like oils havingconjugated double bonds or mixtures thereof may be used, the choicedepending primarily on the availability and cost. Those skilled in theart will understand that the Castung Z-3 used in Example III is acommercial grade of dephthalic, tartaric, citric and malic may besubstituted for the maleic acid or anhydride, although the rosinmodified maleic acid resin is preferred from among the alkyd resins.Likewise, other phenol-aldehyde resins may be used in place of theAmberol and Durez resins hitherto mentioned.

Furthermore, natural resins such as Congo, 7

kauri, Batu, Zanzibar, oil soluble Manila, pontianak, etc., may beemployed but where such natural resins are used they should first be runto make them oil soluble and the first step of the process hereinbeforedescribed wouldhave to be altered accordingly. In such case, the resinwould first be fused, the first portion of the oiladded to it, and thetemperature raised to a point suflicient to dissolve the resin in theoil, after which the second portion of the oil would be added and thewhole then submitted to the blowing step. The necessity for pretreatingthe natural resin will be fully appreciated by those skilled in the art.

The products resulting from the practice of Examples II and III areadapted for use as clear wrinkle finishes without further treatment;however, the product of Example I does not include the required metallicdrier and has a consistency greater than permissible for properspraying. A suitable wrinkle coating composition could be prepared fromthe product of Example I as follows:

Example IV Another type of drier suitable for use in Example IV may beprepared as follows;

Example V I Cobalt linoleate solid -1 lbs 12:16 China wood oil fattyacids do 8-10 Toluol, xylol, petroleum naphtha,

etc gals 6- 8 It will be understood that metal driers other than cobaltcompounds may be used such as those of manganese. The inherentcharacteristic of the drier to be used is its ability to bring about arapid formation of a skin on the exposed surface of th film in order tocause the changes in volume between the surface of the film and theinterior thereof which lead to the production of a wrinkle surface.

The wrinkle coating compositions of Examples II, III and IV may befurther compounded with pigment ground in oil vehicle for the purpose ofproducing wrinkling enamels, and texture modifying ingredients may beadded thereto. Such pigments and texture modifying ingredients, as wellas other driers which may be substituted for that used in the examples,are broadly disclosed in my copending applications Serial Nos. 271,590,now Patent No. 2,294,703; 271,591, now Patent No. 2,344,189; and271,592, filed May 3, 1939; Serial Nos. 297,162, 297,163, now Patent No.

2,268,002; and 297,164, now Patent No. 2,275,239,

filed September 29, 1939; and Serial No. 421,769, filed December 5,1941.

Wrinkle coating compositions such as that of Example IV produced usingthe wrinkle varnish base of my invention are adapted to be sprayed andthen baked at temperatures of from 200 to 250 F. for approximately onehour to produce a wrinkle finish characterized by its toughness andhardness.

It will be understood that While I have set forth certain specificembodiments of my invention, it is not my intention to have my inventionlimited to or circumscribed by the specific details of procedure andproportions indicated in view of the fact that my invention is adaptedto changes according to individual preference and "conditions withoutdeparting from the scope thereof as defined in the appended claims.

I claim:

1. The method of making wrinkle varnish base which consists in meltingan oil-soluble rosinmodified phenol-aldehyde resin in linseed oil at atemperature of approximately 580 F., adding an additional quantity oflinseed oil to the melt and maintaining the temperature at approximately400 F., and then blowing the resulting product with air whil maintainingsaid product at a temperature of approximately 375 to 400 F. until apredetermined desired viscosity or body is obtained.

2. The method of making wrinkle varnish base which consists in meltingan oil-soluble rosinmodified phenol-aldehyde resin in unblown fattydrying oil at a temperature of approximately 580 F., adding anadditional quantity of unblown fatty drying oil to the melt andmaintaining the temperature at approximately 400 F., and then blowingthe resulting product with air while maintaining said product at atemperature of approximately 375 F. to 400 F. until a predetermineddesired viscosity or body is obtained.

WILLIAM A. WALDIE.

